Method of converting an ammonium petroleum sulfonate to barium sulfonate



United States Patent METHOD OF CONVERTING AN AMIVIONIUM PETROLEUM SULFONATE TO BARIUM SULFONATE No Drawing. Application July 8, 1952, Serial No. 297,754

2 Claims. (Cl. 252-33) Our invention relates to the production of concentrates of barium sulfonates in petroleum oils. More particularly, our invention relates to an improved method of converting ammonium petroleum sulfonates to barium petroleum sulfonates. Barium petroleum sulfonates are particularly valuable as addends for lubricating oils in which they act as corrosion inhibitors and efiective detergents.

Pending application Serial No. 297,753 filed July 8, 1952, of Lee V. Brown discloses a process for the production of petroleum oil concentrates of barium sulfonates. The process comprises ammoniating an acid petroleum oil and treating the ammoniated oil with a solvent composed of water and a Water soluble lower aliphatic alcohol, e. g. isopropyl alcohol, of a concentration of about to 70 per cent isopropyl alcohol and at a solvent to oil ratio of 0.3 to 3.1. An alcohol soluble phase (extract) is recovered which contains ammonium sulfonates. The ammonium sulfonates are then reacted at a temperature of 175 to 250 F. with a barium compound, e. g. barium oxide or hydroxide, to produce barium petroleum sulfonates. The reaction may be carried out with the dilute alcohol solution of ammonium sulfonates (extract) or with a concentrated solution obtained by topping the extract. When the extract is used the resulting barium sulfonate solution is concentrated by heating to remove alcohol and water.

We have found, however, that in the conversion of ammonium sulfonates to barium sulfonates an unfilterable haze develops in the product when barium oxide or hydroxide comes into contact with an ammonium sulfonate mixture containing alcohol, e. g. isopropyl alcohol, during the reaction. The haze makes the product particularly undesirable for use as a lubricating oil blending agent as the lubricating oil blend has a hazy appearance that detracts from its marketability. Moreover, the barium sulfonates prepared in this manner often cause an undesirable precipitate to form when they are added to lubricating oil.

We have now found that reducing the amount of alcohol in ammonium sulfonates, obtained by aqueous alcohol extraction of an ammoniated acid petroleum oil, so that it is essentially alcohol-free, e. g. less than about 1 per cent isopropyl alcohol, and reacting this essentially alcohol-free concentrate with barium oxide or hydroxide produces desirable haze-free barium sulfonates that do not form precipitates with lubricating oil. The amount of alcohol is reduced by heating, advantageously flash distilling, the ammonium sulfonate solution to about 200 to 250 F. until the alcohol content is less than about 1 per cent. The bottoms from the flash distillation may, if desired, be steam stripped to insure a concentrate of less than 1 per cent alcohol.

We have also found that when barium oxide or hydroxide is added to an essentially alcohol-flee concentrate of ammonium sulfonates a viscous and even rubbery mixture forms that prevents proper stirring and eflicient reaction. This appears to be due to the formation of 2,727,861 Patented Dec. 20, 195 5- viscous neutral barium sulfonates. We have found, however, that adding the essentially alcohol-free concentrate of ammonium sulfonates slowly to the barium oxide or hydroxide avoids viscous mixtures and produces an eflicient reaction. It appears that the excess of barium compound causes the reaction to proceed directly to the formation of less viscous basic sulfonates.

According to the method of our invention, we heat an alcohol solution of ammonium sulfonates, obtained by extraction of an ammoniated acid oil with a solvent composed of alcohol, e. g. isopropyl alcohol, and water, to a temperature of about 200 to 250 F. until essentially all the isopropyl alcohol is removed. Advantageously, the solution is first heated to about 200 F. and then the heated solution is flash distilled at a temperature of about 200 to 250 F. until essentially all the isopropyl alcohol is removed. The alcohol is recovered and also most of the water is removed. We have found that it is advantageous to remove essentially all water from the ammonium sulfonates to eliminatehandling problems. Ammonium sultonates containing more than about 1 per cent of water are more viscous and harder to handle. The bottoms from the alcohol removal step may then be steam stripped to insure the removal of essentially all of the alcohol. A concentrate of ammonium sulfonates in petroleum oils that is essentially isopropyl alcohol-free, e. g. less than about 1 per cent, is recovered and reacted at a temperature of about to 250 F. with barium oxide or bydroxide, either dry or in solution.

Advantageously, a slurry is prepared by adding barium oxide to water. The barium oxide forms barium hydroxide and the heat of formation is efiectively utilized to maintain the temperature in the reaction zone at about 175 to 250 F., thereby substantially reducing the supply of heat required and correspondingly reducing heat transfer surface requirements. The essentially alcohol-free ammonium sulfonate concentrate is then added slowly to and intimately admixed with the slurry. The reactants are digested for about 1 hour at a temperature of about 175 to 250 F. The barium sulfonate solution formed is then dehydrated to about 300 F. Ammonia is removed and recovered. The solution is filtered while hot to separate excess barium oxide or hydroxide and the filtrate is recovered as a haze-free petroleum oil concentrate of barium sulfonates of high quality and concentration.

By the method of our invention the reaction proceeds smoothly, avoiding viscous reaction mixtures that prevent efiicient reaction and cause handling problems. Moreover, a haze-free barium sulfonate is produced that is highly desirable for use as a lubricating oil blending agent. The product of our invention forms clear solutions with lubricating oils, that are free of precipitates, and which are of superior marketability.

The method of our invention will be further illustrated by the following example.

Example Tests were run on the conversion to barium sulfonates of ammonium sulfonate solutions obtained by isopropyl alcohol and water extraction of an ammoniated acid petroleum oil.

In tests 1 to 3 inclusive, the conversion was carried out in the presence of some alcohol.

In test 1, a decanted solution of barium oxide in 3 /2 parts of water was added to an alcohol solution of ammonium sulfonates (extract) at 170 F. The mixture was digested for 2.3 hours at 180 F. and stirred easily. The mixture was then dehydrated to 300 F. The filtering speed was rapid. The product contained 14.5 per cent barium, had a base number of 51.9, an O. D. color of 865 and was hazy.

dry barium oxide was added to the topped extract at 150 F. with 25 per cent isopropyl alcohol (based on the extract) as a diluent. The mixture was digested for 1.3 hours at 155 F. and stirred easily. The mixture was thendehydrated to 300 F. The filtering speed was slow and the product was cloudy.

Other tests were run on an extract which had been topped to a temperature ofv208 to 250 F. to remove essentially all the alcohol present. These tests were 4 and 5.

In test 4, the extract was topped to a temperature of 208 F. and a solution of. barium oxide in 3% parts of water was added to the resulting concentrate at a temperature of 200 F. The mixture was digested for one hour at 200 F. The mixture formed a stiff emulsion during the. digestion period. The mixture was then dehydrated to 300 F. The filtering speed was rapid and the product was clear. vThe product contained 17.2 per cent barium and had a base number of 73.4 and an O. D. color of 1220.

In test 5, the extract-was topped to a temperature of 250 F., and the resulting concentrate was added to a slurry of barium oxide in 1 part of water over 30 minutes at 190 F. The mixture was digestedfor 1 hour at 190 F. and stirred easily. The mixture was then. dehydrated to 300 F. The filtration was rapid and the product was clear. The product contained 14.9 per cent barium and hada base number of 59.1 and an O. D. color oi 1322.

- The results of tests 1 to 3 show that a hazy product resulted when barium oxide was reacted with ammonium sulfonates in the presence of isopropyl alcohol. The results'of tests 4 and 5 show, however, that when essentially all the alcohol was removed from the ammonium sulfonatesolution and when no alcohol was present in the reaction with barium oxide 9. clear desirable product was obtained.

The'results of test 4 show that a stifi emulsionformed when a barium oxide slurry was added to the concentrated ammonium sulfonate solution, apparently due to the formation of viscous neutral sulfonates. The results of test 5 show, however, when the concentrated ammonium sulfonate solution was added to a barium oxide 4. slurry no emulsions were formed and the mixture stirred easily, apparently due to the formation of less viscous basic sulfonates.

Therefore, these tests show that to obtain a clear product and to avoid reaction difiiculties essentially all the alcohol must be removed from the ammonium sulfon'ate solution and the reaction must be carried out by adding the solution slowly to the barium oxide slurry.

We claim:

1. In the conversion of ammonium petroleum sulfonates, obtained by isopropyl alcohol and water extraction of an ammoniated acid petroleum oil, to barium petroleum sulfonates, the method of producing hazefree petroleum oilv concentrates of barium sulfonates which comprises heating the ammonium sulfonates to a temperature of about 200 to 250 F. until the isopropyl alcohol content is less than about 1 per cent, recovering isopropyl alcohol, adding the resulting essentially isopropyl alcohol-free concentrate of ammonium su l'fonates to and intimately admixing it'with a barium compoundinwhich the barium is in combination. with a group selected from oxy and hydroxyl groups while maintaining. the tempera ture at about 175 to 250 F. and separating a hazefree concentrate of barium sulfonates in petroleum oils.

2. In the conversion of ammonium petroleum sulfonates, obtained-by isopropyl alcohol and water extraction of an ammoniated acid petroleum oil to barium petroleum sulfonates, the method of producingv hazefree petroleum oil concentrates of barium sulfonates which,

References Cited in the file of this patent UNITED STATES PATENTS- 1,707,l87 Cobb Mar. 26, 1929 1,811,535 Buc June 23, 1931 2,097,440 Blumer Nov. 2, 1937 2,413,311 Cohen Dec. 31, 1946' 2,418,894 McNab .Apr. 15, 1947 2,509,863 Harlan May 30, 1950 2,559,439 Jones July 3, 1951 2,632,694

Watkins Mar. 24, 1953 

1. IN THE CONVERSION OF AMMONIUM PETROLEUM SULFONATES, OBTAINED BY ISOPRROPYL ALCOHOL AND WATER EXTRACTION OF AN AMMONIATED ACID PETROLEUM OIL, TO BARIUM PETROLEUM SULFONATES, THE METHOD OF PRODUCING HAZE-FREE PETROLEUM OIL CONCENTRATES OF BARIUM SULFONATES WHICH COMPRISES HEATING THE AMMONIUM SULFONATES TO A TEMPERATURE OF ABOUT 200* TO 250* F. UNTIL THE ISOPROPYL ALCOHOL CONTENT IS LESS THAN ABOUT 1 PER CENT, RECOVERING ISOPROPYL ALCOHOL ADDING THE RESULTING ESSENTIALLY IOSPROPYL ALCOHOL-FREE CONCENTRATED OF AMMONIUM SULFONATES TO AND INTIMATELY ADMIXING IT WITH A BARIUM COMPOUND IN WHICH THE BARIUM IS IN COMBINATION WITH A GROUP SELECTED FROM OXY AND HYDROXYL GROUPS WHILE MAINTAINING THE TEMPERATURE AT ABOUT 175* TO 250* F. AND SEPARATING A HAZEFREE CONCENTRATE OF BARIUM SULFONATES IN PETROLEUM OILS. 